CN117794983A

CN117794983A - High molecular weight polyesteramides

Info

Publication number: CN117794983A
Application number: CN202280055489.5A
Authority: CN
Inventors: 亚里士多德·卡拉吉安尼斯; 郑品官; 斯科特·埃勒里·乔治; 奥利维尔·艾蒂安·希拉尔·吉尔特·维尔金德仁; 金·纳兹·罗斯玛丽·杜莫莱因; 约书亚·赛斯·坎农; 张璞; 汗·杜克·德兰
Original assignee: Solutia Inc
Current assignee: Solutia Inc
Priority date: 2021-08-19
Filing date: 2022-08-03
Publication date: 2024-03-29
Also published as: WO2023023446A1

Abstract

The present invention provides certain polyesteramide compositions having glass transition temperatures (T _g ) Greater than or equal to 0deg.C. The polyesteramides of the invention are useful as polymer interlayers for laminated structures such as safety glass, where excellent toughness is combined with high adhesion to glass.

Description

High molecular weight polyesteramides

Technical Field

The present invention relates generally to the field of polymer science. More particularly, the present invention relates to high molecular weight polyesteramides which are particularly useful as polymer interlayers in laminated structures.

Background

Thermoplastic polymers are useful in a wide variety of applications, including: for example, various electrical, automotive, medical, consumer, industrial, and packaging applications. Thermoplastic polymers are preferred over thermoset plastics in that they can be readily melt processed into a variety of useful articles.

Each type of thermoplastic polymer has different characteristics, which makes it desirable for certain end uses. Elastomeric thermoplastic polymers typically have glass transition temperature values below room temperature and low modulus values, making them suitable for applications requiring flexibility and stretchability. In contrast, rigid thermoplastic polymers generally have glass transition temperature values and high modulus values above room temperature, which makes them suitable for applications requiring hardness and strength.

Polyester amides are a class of thermoplastic polymers formed by polycondensation of diacids, diols, and diamines (see, e.g., WO2008112833, U.S. Pat. nos. 5,672,676 and 2,281,415, and CA 2317747). Polyester amides are of great industrial interest, mainly due to their excellent heat resistance properties (see us patent No. 5,672,676), their processing suitability (amenability) and their biodegradability potential (see WO 2008112833).

The polymer sheet may be used as an interlayer in a multi-layer panel, formed by sandwiching the interlayer between two sheets of rigid, transparent material such as glass. Such laminated multi-layer panels are commonly referred to as "safety glass" and are used in both architectural and automotive applications. One of the main functions of the interlayer in a safety glass panel is to absorb energy generated by an impact on the panel without allowing objects to penetrate the glass. The interlayer also helps to maintain the bond of the glass when sufficient force is applied to break the glass, so as to prevent the glass from forming sharp fragments and shattering. In addition, the interlayers can provide laminated panels having higher acoustic barrier properties, reduce Ultraviolet (UV) light and/or Infrared (IR) light transmission through the panels, and enhance their aesthetic appeal by the addition of color, texture, and the like.

In general, when a polymer interlayer exhibits desirable properties (e.g., stiffness), it may lack other desirable or important properties such as impact resistance or optical clarity. In some applications, a safety glass panel may be used as a structural element, but it may also be desirable to impart aesthetic properties to the application. In this case, optimal optical properties, rigidity and impact resistance are not only desired, but also required. Unfortunately, as the stiffness of conventional interlayers increases, the impact resistance of the resulting panels generally becomes worse. Similarly, conventional interlayers formulated for enhanced impact strength typically lack the necessary rigidity required in many applications, such as applications requiring excellent structural support characteristics.

The emerging market for architectural laminated glass requires interlayers having structural characteristics such as load carrying capability. The interlayer is Eastman's Saflex ^TM DG structural interlayer consisting of plasticized polyvinyl butyral (polyvinyl butyral, "PVB"). Typically, structural interlayers are stiffer products than standard PVB interlayers, and such higher stiffness allows laminates made with the structural interlayers to withstand higher loads. Alternatively, a structural interlayer may be used to allow for reduced glass thickness while achieving the same laminate support Load carrying capacity.

With the advent of more applications requiring stiffer interlayers (e.g., single sided balcony laminates, canopies, stairways, and support beams), higher performance structural interlayers are desired. However, some commercially available interlayers suffer from drawbacks in terms of processability and/or functionality. Furthermore, in many of these structural applications, the attractive force of glass is the transparency of the glass panel. Thus, the layers or interlayers must also not interfere with the optical properties of the structural glass article into which they are incorporated.

In addition, lighter weight and/or lower cost laminates are desirable for many applications. These lighter weight laminates must still have desirable physical and optical properties, such as impact protection, clarity, and other properties. One way to obtain a lighter weight laminate is to reduce the thickness of the glass. However, if the thickness of the glass is reduced too much, the rigidity of the laminate may be impaired. A higher stiffness interlayer can then be used to restore the partially lost stiffness and give a lighter weight but acceptable performance laminate. Another approach to reduce the weight of the laminate is to eliminate one or more sheets of glass and replace them with rigid, transparent, plastic panels of sufficiently high rigidity to maintain the integrity of the laminate as well as the desired optical properties.

Thus, there is a need for polymer interlayers that exhibit strength and rigidity while still providing adequate impact resistance. Ideally, such interlayers will also exhibit desirable optical properties, such as low haze and non-yellowing. Ideally, these interlayers can be used in multiple layer panels for a wide variety of applications, including construction applications, and will provide an optimized balance of structural and optical properties as well as aesthetic characteristics.

Disclosure of Invention

There is a continuing need for polymers with excellent toughness and clarity to improve glass interlayers. The polyester amide (PEA) of the present invention combines the toughness of polyesters with the adhesive properties of polyamides, as described below. Obtaining high molecular weights in the melt phase process for making polyester amides is problematic because there is little end group residue and stoichiometric control of the non-volatile diacids, diamines, and diols becomes impractical. The addition of branching agents and/or crosslinking agents generally results in a broad molecular weight distribution and more brittle polymers. We have found that the use of certain chain extenders provides improved polyesteramide compositions having desirable characteristics which react with a plurality of available functional groups without concomitant excessive branching of the polymer experienced by the branching compound and/or crosslinker.

In summary, the present invention provides certain polyesteramide compositions having glass transition temperatures (T _g ) Greater than or equal to 0deg.C. The polyesteramides of the invention are useful as polymer interlayers for laminated structures such as safety glass, wherein excellent toughness is combined with high adhesion to glass.

Accordingly, in a first aspect, the present invention provides a polyesteramide composition comprising the following residues:

a. at least one diacid;

b. about 10mol% to about 90mol% glycol;

c. about 10 mole% to about 90 mole% of a diamine; optionally, a third layer is formed on the substrate

d. A polyfunctional reactant having at least three functional groups selected from carboxylic acid, amine, and hydroxyl groups;

wherein the sum of diacid equivalents is about 100 mole percent and the sum of diol and diamine equivalents is about 100 mole percent; and

e. about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl groups, based on the total weight of the polyesteramide composition consisting of a, b, c, and optionally d, and wherein the polyesteramide composition exhibits an inherent viscosity of about 0.6dL/g to about 2.0 dL/g.

In the present invention, components a, b, c, and e are present in the polyesteramide composition, only component d is an optional component.

In addition, the polyesteramide compositions of the invention may be used to make shaped or formed thermoplastic articles. Thus, in a second aspect, the present invention provides the polyester amide composition of the present invention in the form of a shaped or formed article. In one embodiment, the shaped or formed article is a film or sheet.

In a third aspect, the present invention provides an interlayer comprised of the polyesteramide composition of the invention.

In a fourth aspect, the present invention provides an interlayer of the present invention disposed between two panels, thereby forming a laminated structure.

Drawings

Fig. 1 is a graph of current/rpm ratio for batches prepared with and without chain extender corresponding to example 2 (comparative) and example 3.

Detailed Description

Definition:

as used herein, the term "diacid" or "dicarboxylic acid" refers to aliphatic, cycloaliphatic, and aromatic dicarboxylic acids. In one embodiment, the dicarboxylic acid is selected from aliphatic dicarboxylic acids having 3 to 36 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms, and aromatic dicarboxylic acids having 8 to 16 carbon atoms. Exemplary dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid (sebasic acid), sebacic acid (decanedioic acid), dodecanedioic acid, glycolic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, octadecanedioic acid, and 2, 6-naphthalenedicarboxylic acid. Since the term refers to dicarboxylic acid residues in the polyesteramide, the term "dicarboxylic acid" also includes the corresponding esters, anhydrides, and acid chlorides.

In one embodiment, the diacid includes a longer carbon chain species commonly referred to as "dimer acid", such as may be under the trade name Pripol ^TM Those commercially available from Croda, and use product names 1010, 1006F, 1009F, 1010F, 1009, and 1012. Exemplary dimer acids include the following: 9- [ (Z) -non-3-enyl]-10-octyl nonadecanoic acid; and 9-nonyl-10-octyl nonadecanedioic acid (a hydrogenated dimer acid, pripol) ^TM 1009). Dimer acid was designated CAS number 61788-89-4 and hydrogenated version was designated CAS number 68783-41-5.

Dimer acid is usually obtained from Diels-Alder synthesis reactions applied to unsaturated fatty acids, mainly from tall oil, oleic acid, rapeseed oilAnd cottonseed oil. Commercial products having 36 carbon atoms (C36) are obtained from unsaturated C18 acids, which are typically tall oil components, and the structure of the resulting dimer acid is shown in the following figures. Various grades are available, such as the Unidyme of Kraton ^TM Wherein distillation can be used to increase dimer content compared to monomer and trimer species. Hydrogenation grades are also available in which the colour is reduced and the residual double bonds are removed. Although C36 is most common, other chain lengths are also commercially known, for example under the trade name radio acid ^TM 0994C 44 supplied from Oleon.

In another embodiment, the term "diacid" or "dicarboxylic acid" may include (i) additional heteroatoms, such as sulfur, in addition to the oxygen atoms comprising the carboxyl moiety, or (ii) one or more olefin moieties. Exemplary compounds in this example include t-butyl isophthalic acid, 5-hydroxy isophthalic acid, fumaric acid, maleic acid, itaconic acid, and 4,4' -sulfonyldibenzoic acid. In certain embodiments, the diacid or dicarboxylic acid is free of unsaturation or olefinic bonds.

As used herein, the term "diol" refers to aliphatic diols, cycloaliphatic diols, and aralkyl diols. Exemplary diols include ethylene glycol, 1, 2-propanediol (also known as propylene glycol), 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, 2, 4-tetramethyl-1, 3-cyclobutanediol, isosorbide, p-xylylene glycol (p-xylylendol), and the like. These diols may also contain ether linkages, for example in the case of diethylene glycol, triethylene glycol and tetraethylene glycol. Other examples of diols include high molecular weight homologs known as polyethylene glycols, e.g., in Carbowax ^TM Trade names are those produced by the dow chemical company (Dow Chemical Company). In one embodiment, the polyethylene glycol has a molecular weight of greater than 200 daltons to about 10,000 daltons (Mn). These diols also includeHigher alkyl analogs such as dipropylene glycol, dibutylene glycol, and the like. Similarly, other diols include higher polyalkylene ether diols such as polypropylene glycols and polytetramethylene glycols having a molecular weight of from about 200 daltons to about 10,000 daltons (Mn) (also referred to as g/mol).

As used herein, the term "diamine" refers to an alkylene diamine, a cycloalkylene diamine, an aryl alkylene diamine, or an arylene diamine. In one embodiment, these diamines include alkylene diamines having 2 to 12 carbon atoms, cycloalkylene diamines having 6 to 17 carbon atoms, and aromatic diamines having 8 to 16 carbon atoms. Exemplary diamines include 1, 2-ethylenediamine, 1, 6-hexamethylenediamine, 1, 4-cyclohexanediamine and 1, 3-cyclohexanediamine, 1, 4-cyclohexanedimethylamine and 1, 3-cyclohexanedimethylamine, 4 '-methylenebis (cyclohexylamine), 4' -methylenebis (2-methylcyclohexylamine) and 2, 4-tetramethyl-1, 3-cyclobutanediamine, 2, 4-trimethylhexamethylenediamine, 4-oxaheptane-1, 4-diamine, 4, 7-dioxadecane-1, 10-diamine, 1, 4-cyclohexanedimethylamine, 1, 3-cyclohexanedimethylamine, 1, 7-heptamethylenediamine, 1, 12-dodecamethylenediamine, and the like.

As used herein, the term "polyfunctional reactant having at least three functional groups" refers to a polyfunctional compound having at least three functional groups that result in branching in the polyesteramide structure. These relatively small amounts of branching agent compounds were found to promote molecular weight increase kinetics in the practice of the present invention. In one embodiment, such polyfunctional reactants are used at a level of less than or equal to about 1.0 mole percent. Exemplary polyfunctional reactants include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, pyromellitic acid, pentaerythritol, glycerol, trimethylol propane (TMP), trimethylol ethane (TME), erythritol, threitol, dipentaerythritol, sorbitol, dimethylol propionic acid, and the like. In one embodiment, the polyfunctional reactant is trimethylol propane.

"chain extenders" as used herein are selected from compounds capable of reacting with one or more of the available end groups found in polyesteramides, in particular carboxyl, hydroxyl and amino groups. In certain embodiments, the polyester amide obtained using the chain extender has a polydispersity (Mw/Mn) of less than about 6, less than about 5, or less than about 4. Exemplary chain extender species include diepoxides, diisocyanates, biscaprolactam, bisoxazolines, carbodiimides, and dianhydrides. In another embodiment, the chain extender has three or more groups (i.e., multifunctional) selected from carboxyl, hydroxyl, and amino groups. The intended function of the chain extender may be achieved (i) during the polyester amide synthesis process or (ii) at the end of the polyester amide synthesis process, or (iii) by melt mixing techniques and equipment such as LIST kneaders, brabender mixers or single-screw or twin-screw extruders.

As used herein, the term "residue" refers to a monomer unit or a repeat unit in a polymer, oligomer, or dimer. For example, the polymer may be prepared from the condensation of the following monomers: terephthalic acid ("TPA") and cyclohexyl-1, 4-dimethanol ("CHDM"). The condensation reaction results in the loss of water molecules. Residues in the resulting polymer are derived from terephthalic acid or cyclohexyl-1, 4-dimethanol.

The polymer may also be functionalized with other reactants (e.g., epoxide, isocyanate, etc.) during and after the polymerization reaction. The reactants introduced are also considered residues.

As used herein, the term "alkyl" shall mean a hydrocarbon substituent. Alkyl groups suitable for use herein may be linear, branched or cyclic, and may be saturated or unsaturated. Carbon units in alkyl groups are typically included; for example C ₁ -C ₆ An alkyl group. Alkyl groups suitable for use herein include any C ₁ -C ₂₀ 、C _1- C ₁₂ 、C ₁ -C ₅ Or C ₁ -C ₃ An alkyl group. Specific examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, and dodecyl. As used herein, the term "alkylene" refers to a divalent alkyl group, e.g.) CH ₂ - (methylene).

"cycloalkyl" refers to a cyclic alkyl group having at least three carbon units, e.g., C _3- C ₈ Cycloalkyl groups. The number of carbon units in cycloalkyl groups is generally included. Non-limiting examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, and the like.

"bicycloalkyl" refers to a ring system having two cycloalkyl rings. The bicycloalkyl ring system may be bridged or unbridged. The number of carbon units may be specified (e.g. C ₆ -C ₁₇ )。

"heterocyclyl" refers to a ring system containing one or more heteroatoms (e.g., N, O and S). The number and type of heteroatoms may be specific. The dimensions of the ring may also be specific. One example includes 6-to 8-membered heterocyclic groups containing 2N heteroatoms. Examples of heterocyclyl groups include piperidinyl, piperazinyl and pyrrolidine.

By "amorphous" is meant that the material does not exhibit a melting point by dynamic scanning calorimetry (dynamic scanning calorimetry, "DSC") after a scanning procedure consisting of: the temperature range covered by the scan is-50 ℃ to 300 ℃ by cooling from the molten state (i.e. typically in the region of 280 ℃ to 300 ℃) at a typical slope of 20 ℃/min (cooling and heating) under nitrogen atmosphere, and heating.

By "semi-crystalline" is meant that the material exhibits a melting point detectable by DSC after a scanning procedure consisting of: the temperature range of the scanning cover is-50 ℃ to 300 ℃ cooled from the molten state (i.e. typically in the region of 280 ℃ to 300 ℃) and heated at a typical slope of 20 ℃/min (cooling and heating) under nitrogen atmosphere.

As used herein, the term "parts per hundred resin" or "phr" refers to the amount of plasticizer present per hundred resin on a weight basis. For example, if 30 grams of plasticizer were added to 100 grams of resin, the plasticizer content would be 30phr. If the polymer layer includes two or more resins, the weight of plasticizer is compared to the total amount of all resins present to determine the parts per hundred resin. Further, when the plasticizer content of a layer or interlayer is provided herein, it is provided with reference to the amount of plasticizer in the mixture or melt used to prepare the layer or interlayer, unless otherwise indicated.

Alkanedioic acid; such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, octadecanedioic acid or icosanedioic acid; may have a terminal carboxylic acid or an internal carboxylic acid. For example, pimelic acid may be 1, 7-pimelic acid, 1, 6-pimelic acid, 1, 5-pimelic acid, 1, 4-pimelic acid, 2, 6-pimelic acid, 3, 5-pimelic acid, or the like. The alkane groups may be unbranched or branched. For example, pimelic acid may be 2-methylhexanedioic acid, 3-methylhexanedioic acid, 2-ethylpentanedioic acid (2-ethylpendanedioic acid), etc.

One class (a) of carbonyl bislactams mentioned herein has the formula:

wherein m is an integer of 3 to 15. In certain embodiments, m is 5-12.

Another class (B) of biscaprolactam referred to herein has the formula:

wherein m is 2-20.

Another class of (C) biscaprolactam referred to herein has the formula wherein the divalent linking group is (i) a 3-20 or 5-12 cycloaliphatic ring, or (ii) an aromatic ring selected from phenylene and naphthylene:

in one embodiment, the divalent linking group is a 1, 4-phenylene group, as shown in the following examples of class (C):

in certain embodiments, the diepoxide mentioned above has the following general formula (D):

wherein n is 0 to 100.

An example of a compound of formula (D) is EPONEX ^TM 1510 resins available from Hexion (where n=0).

The compounds of formula (D) may be obtained, for example, from the reaction product of bisphenol a and epichlorohydrin followed by hydrogenation. In general, diglycidyl ethers of bisphenols are known which can be used analogously for the synthesis of other compounds of formula (A).

In one embodiment, aromatic epoxides may be used, but are less desirable for certain applications where UV resistance is desired.

The diepoxides mentioned herein also include other known epoxides, such as:

As mentioned herein, bisoxazolines have the following general formula:

wherein n is 1 or 2 and R is a divalent C ₂ -C ₂₀ Alkyl, C ₅ -C ₁₂ A cycloaliphatic group, or a group of the formula:

(i.e., phenylene or naphthylene).

In a first aspect, the present invention provides a polyesteramide composition comprising the following residues:

a. at least one diacid;

b. about 10mol% to about 90mol% of at least one glycol;

c. about 10 mole% to about 90 mole% of at least one diamine; optionally, a third layer is formed on the substrate

d. A polyfunctional compound having at least three functional groups selected from carboxylic acid, amine, and hydroxyl groups;

e. about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl groups, based on the total weight of the polyesteramide consisting of a, b, c, and optionally d, wherein the polyesteramide composition exhibits an inherent viscosity of about 0.6dL/g to about 2.0dL/g.

In some embodiments of the present invention, in some embodiments, the polyester amide composition will exhibit an inherent viscosity of from about 0.6dL/g to about 1.8dL/g, from about 0.6dL/g to about 1.6dL/g, from about 0.6dL/g to about 1.4dL/g, from about 0.6dL/g to about 1.2dL/g, from about 0.6dL/g to about 1.0dL/g, from about 0.6dL/g to about 0.8dL/g, from about 0.8dL/g to about 1.0dL/g, from about 0.8dL/g to about 1.2dL/g, from about 0.8dL/g to about 1.6dL/g, from about 0.8dL/g to about 1.8dL/g, from about 0.8dL/g to about 2.0dL/g, from about 1.0dL/g to about 1.2dL/g about 1.0dL/g to about 1.4dL/g, about 1.0dL/g to about 1.6dL/g, about 1.0dL/g to about 1.8dL/g, about 1.0dL/g to about 2.0dL/g, about 1.2dL/g to about 1.4dL/g, about 1.2dL/g to about 1.6dL/g, about 1.2dL/g to about 1.8dL/g, about 1.2dL/g to about 2.0dL/g, about 1.4dL/g to about 1.6dL/g, about 1.4dL/g to about 1.8dL/g, about 1.4dL/g to about 2.0dL/g, about 1.6dL/g to about 1.8dL/g, about 1.6dL/g to about 2.0dL/g, or about 1.8dL/g to about 2.0dL/g.

In certain embodiments, the polyester amide has a number average molecular weight (Mn) greater than about 10,000, greater than about 20,000, greater than about 30,000, or greater than about 40,000. In certain embodiments, the Mn will be less than about 100,000, less than about 90,000, less than about 80,000, less than about 70,000, less than about 60,000, or less than about 50,000 daltons.

In one embodiment, the diacid is selected from aliphatic dicarboxylic acids having 3 to 20 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms, and aromatic dicarboxylic acids having 8 to 16 carbon atoms.

In one embodiment, the diacid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid, glycolic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and 2, 6-naphthalenedicarboxylic acid.

In one embodiment, the diacid is selected from 9- [ (Z) -non-3-enyl ] -10-octyl nonadecanoic acid; and 9-nonyl-10-octyl nonadecanoic acid.

In one embodiment, the diol is selected from the group consisting of aliphatic diols, cycloaliphatic diols, and aralkyl diols.

In one embodiment, the glycol is selected from ethylene glycol; 1, 2-propanediol; 1, 3-propanediol; 1, 4-butanediol; 1, 5-pentanediol; 1, 6-hexanediol; 2, 2-dimethyl-1, 3-propanediol; 1, 2-cyclohexanedimethanol; 1, 3-cyclohexanedimethanol; 1, 4-cyclohexanedimethanol; 2, 4-tetramethyl-1, 3-cyclobutanediol; isosorbide; p-dibenzyl alcohol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol; dipropylene glycol; a dibutylene glycol; polyalkylene ether glycols selected from polypropylene glycol and polytetramethylene glycol.

In one embodiment, the diamine is selected from the group consisting of alkylene diamines having 2 to 12 carbon atoms, cycloalkylene diamines having 6 to 17 carbon atoms, and aromatic diamines having 8 to 16 carbon atoms.

In one embodiment, a polyfunctional reactant is present and is selected from trimellitic acid, trimellitic anhydride, trimesic acid, pyromellitic dianhydride, pentaerythritol, glycerol, trimethylol propane, trimethylol ethane, erythritol, threitol, dipentaerythritol, sorbitol, and dimethylol propionic acid.

In one embodiment, the chain extender is selected from the group consisting of difunctional compounds selected from the group consisting of diepoxides, diisocyanates, biscaprolactam, bisoxazolines, carbodiimides, and dianhydrides.

In certain embodiments, the polyesteramide composition exhibits one or more of the following characteristics: (i) a glass transition temperature of about 0 ℃ to about 200 ℃; (ii) a haze of less than about 2%; and/or (III) impact resistance of at least about 12 feet, characterized by an average fracture height (or fracture height) of the interlayer measured according to ANSI/SAE Z26.1-1996 at a temperature of about 70°f (about 21 ℃) when the interlayer has a thickness of 30 to 60 mils and is laminated between two 2.3mm thick transparent glass sheets. The average fracture height can also be measured at other thicknesses.

In another aspect, the present invention provides a polyesteramide composition comprising the following residues:

a. a diacid selected from sebacic acid and dodecanedioic acid;

b. about 40mol% to about 60mol% 1, 4-cyclohexanedimethanol;

c. about 40mol% to about 60mol% of 4,4' -methylenebis (2-methylcyclohexylamine); and

d. from about 0.1mol% to about 0.5mol% trimethylolpropane;

about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl, based on the total weight of the polyesteramide consisting of a, b, c and optionally d.

The polyesteramides of the invention may be prepared by using a combination of methods known in the art for polyesters and polyamides. In one aspect, the method includes two distinct stages: (A) A combined esterification and amidation stage followed by (B) a polycondensation stage.

The esterification and amidation reactions are advantageously carried out in an inert atmosphere (e.g., N ₂ ) The reaction is carried out at a temperature of 150 to 280 ℃ for 0.5 to 8 hours or at 180 to 250 ℃ for 1 to 4 hours at atmospheric pressure or higher. Depending on its reactivity and the specific process conditions used, the diols and diamines are generally used in molar excess of 1.0 to 4 moles per total moles of diacid monomer. The non-volatile diols and diamines are advantageously added near stoichiometric balance to achieve high molecular weight, while the volatile diols and diamines are to some extent Evaporation, particularly during the vacuum phase, and is typically added in stoichiometric excess.

The second stage polycondensation is typically conducted at a temperature of from about 220 ℃ to about 350 ℃, or from about 230 ℃ to 300 ℃, or from about 240 ℃ to 290 ℃ for 0.1 to 6 hours or 0.25 to 4 hours under reduced pressure. Agitation or other suitable mixing conditions are advantageously used in both stages to ensure adequate heat transfer, mass transfer and surface renewal of the reaction mixture.

Other process variations that may be used are based on known polyester and polyamide synthesis methods. For example, the diamine and diacid may first be combined in the presence of water to form a salt. This is a stoichiometric method commonly used in polyamide synthesis to ensure equilibrium. For polyesteramides having less than 50mol% diamine, carboxyl terminated prepolymers are obtained, wherein diols may be added to obtain high molecular weights before the polycondensation stage is carried out under vacuum. In a similar manner, it is also possible to pre-react the diol and then add the diamine in a separate stage.

Both stages of the reaction are promoted by suitable catalysts, particularly those known in the art and taught, for example, in U.S. Pat. nos. 4,167,395 and 5,290,631, which are incorporated herein by reference. Exemplary catalysts include alkoxy, alkyl, and halogenated titanates; alkali metal hydroxides and alkoxides; an organic carboxylate salt; an alkyl tin compound; metal oxides such as antimony (III) oxide and germanium (IV) oxide; metal acetates such as zinc acetate and aluminum acetate; etc. In some cases, the esterification stage can be autocatalytic when starting materials such as terephthalic acid and isophthalic acid are used. A three-stage manufacturing procedure similar to that of the disclosure of US 5,290,631 (which is incorporated by reference and as herein) may be used, particularly when a mixed monomer feed of acid and ester is used.

a. Chain extension

In order to obtain high molecular weights where the inherent viscosity (IhV) is greater than about 0.8dL/g, there must be little end residue and the stoichiometric imbalance between carboxylic acid and amine + diol end groups will limit the final molecular weight, as shown by the Carother equation:

where DP is the degree of polymerization or the average number of repeat units in the polymer chain, p=the conversion of the stoichiometrically balanced polycondensate. When the stoichiometry is imbalanced, the equation is modified to the form:

where s=stoichiometrically unbalanced (e.g. s=0.98 if 0.98 moles of diacid are combined with 1.0 total moles of diamine+diol). The effect is significant in that the equilibrium stoichiometry at 99% conversion will give a DP of 100 compared to only a 2% excess of diamine + diol (s=0.98) that reduces the DP to 50. In embodiments, the polyester amide has a DP of greater than about 50, greater than about 60, or greater than about 70.

This chain extension process may be particularly advantageous when all components are considered non-volatile, as careful weighing to control the amount of each monomer added is offset by small losses due to degradation, purity and dehydration. In this case, the available acid ends must be reacted with the available hydroxyl or amino ends. Under the process conditions described, the hydroxyl terminus is substantially unreactive with other hydroxyl termini or amino termini, and the carboxyl terminus is unreactive with other carboxyl termini. Advantageously, the preferred compounds will have the ability to react with two or even all three of the essentially available functional groups. More than one chain extender compound having different functional group reactivities may also be used.

The chain extender is generally added after the polycondensation has reached a high conversion, although it is not necessary to wait until the molecular weight increase rate reaches a plateau. The addition of the chain extender earlier can shorten the overall process time. The best results are obtained when the chain extender is miscible with the polyesteramide when added in liquid or solid form. The liquid chain extender may be preheated to reduce viscosity and promote transfer. The solids may also be added as such, melted or pre-dissolved in a suitable solventIs contained in the organic solvent of (a). In this regard, exemplary solvents include toluene, xylene isomers, heptane, tetrahydrofuran, glyme, diglyme, dodecane, isopar ^TM Isoparaffinic solvents and other known solvents that do not have functional groups that react with ester or amide linkages. Thus, although not precluded, alcohols are less preferred because alcohols can react with ester and amide linkages, resulting in reduced molecular weight. Although not excluded, water is not preferred as it generally results in hydrolysis of a certain amount of available ester and amide linkages.

b. Inherent viscosity

The inherent viscosity (IhV) of these polyesteramides is a useful representation of molecular weight and is determined according to ASTM D2857-70 procedure in a Wagner viscometer of Lab Glass company with 1/2mL capillary spheres using a polymer concentration of about 0.5% by weight in 60/40wt% phenol/tetrachloroethane. The procedure was carried out by: the polymer/solvent system was heated at 120 ℃ for 15 minutes, the solution was cooled to 25 ℃ and the flow time at 25 ℃ was measured. The inherent viscosity is calculated by the following formula:

Wherein:

η: an inherent viscosity at 25 ℃ at a polymer concentration of 0.5g/100mL of solvent;

t _S : sample flow time;

t ₀ : solvent blank flow time;

c: polymer concentration in grams/100 mL solvent (0.5)

(the logarithmic viscosity units are expressed in deciliters/gram throughout this application)

In some embodiments, certain agents that color the polymer may be added to the melt, including toners or dyes, in the process for preparing the polyesteramides useful in the present invention. In one embodiment, a blue dye toner (blue toner) is added to the melt to adjust the b-value of the resulting polymer melt phase product. Such blue-dyeing agents include blue inorganic and organic toners and/or dyes. In addition, red toners and/or dyes may also be used to adjust the a-color. In one embodiment, the polymers or polymer blends useful in the present invention and/or the polymer compositions of the present invention (with or without toners) may have color values L, a, and b, as determined using a Hunter Lab Ultrascan Spectra colorimeter manufactured by Hunter Associates laboratories, inc (Hunter Associates Lab inc., reston, va) of leston, virginia. Color measurement is the average of values measured on pellets or powders of polymers or sheets or other articles injection molded or extruded from them, or interlayers laminated with glass. They are determined by the color system of CIE (international commission on illumination) (translation) L x a x b x, where L x denotes the luminance coordinates, a x denotes the red/green coordinates, and b x denotes the yellow/blue coordinates. Organic toners, such as blue and red organic toners, may be used, such as those described in U.S. Pat. Nos.5,372,864 and 5,384,377, the entire contents of which are incorporated herein by reference. The toner may be fed as a premix composition. The premix composition may be a pure blend of red and blue compounds, or the composition may be pre-dissolved or slurried in one of the sources of the polyesteramide (e.g., the diol).

The total amount of toner component added may depend on the amount of yellow inherent in the matrix polyesteramide and the efficacy of the toner. In one embodiment, a combined toner component concentration of up to about 15ppm and a minimum concentration of about 0.5ppm may be used. In one embodiment, the total amount of blue dye additive may be in the range of 0.5ppm to 10 ppm. In one embodiment, the toner may be added to the esterification zone or polycondensation zone. Advantageously, the toner is added to the early stage of polymerization.

The polyesteramides of the invention may be combined or compounded with various additives. The polyesteramide composition may further comprise additives known to those skilled in the art. In one embodiment, the composition further comprises an additive selected from the group consisting of: antioxidants, tackifiers, adhesion control agents, colorants, mold release agents, flame retardants, plasticizers, nucleating agents, UV stabilizers, UV absorbers, heat stabilizers, glass fibers, carbon fibers, fillers, impact modifiers, and silanes (e.g., epoxy or isocyanate silanes). In other embodiments, the composition comprises more than one additive. In certain embodiments, these additives may be present in an amount of about 0.01% to about 25% by weight of the total composition. Examples of commercially available impact modifiers include, but are not limited to, ethylene/propylene terpolymers, functionalized polyolefins such as those containing methyl acrylate and/or glycidyl methacrylate, styrene-based block copolymer impact modifiers, and various acrylic core/shell impact modifiers. The residues of these additives are also considered to be part of the polyesteramide composition. Examples of commercially available impact modifiers are well known in the art and may be used in the present invention, including but not limited to ethylene-co-glycidyl methacrylate based impact modifiers, ethylene/propylene terpolymer based impact modifiers, styrene based block copolymer impact modifiers, and various acrylic core/shell impact modifiers.

Heat stabilizers that are effective in stabilizing polyesteramides during melt processing include, but are not limited to, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, and various esters and salts thereof. The esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. The number of esters present in a particular phosphorus compound may vary from zero to the maximum allowed based on the number of hydroxyl groups present on the phosphorus compound used.

Examples of the heat stabilizer include tributyl phosphate, triethyl phosphate, tributoxyethyl phosphate, t-butylphenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyldimethyl phosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, tri (xylyl) phosphate, t-butylphenyl diphenyl phosphate, resorcinol bis (diphenyl phosphate), tribenzyl phosphate, phenylethyl phosphate, trimethyl thiophosphate, phenylethylthiophosphate. In addition, phosphonates such as dimethyl methylphosphonate, diethyl pentylphosphonate, dilauryl methylphosphonate, diphenyl methylphosphonate, dibenzyl methylphosphonate, diphenyl methylphosphonate, dimethyl methylphosphonate, diphenyl phosphinate, benzyl diphenylphosphinate, methyl diphenylphosphinate, trimethylphosphine oxide, triphenylphosphine oxide, tribenzylphosphine oxide, 4-methyldiphenylphosphine oxide, triethyl phosphite, tributyl phosphite, trilauryl phosphite, triphenyl phosphite, tribenzylphosphine, phenyl diethyl phosphite, phenyl dimethyl phosphite, benzyl dimethyl phosphite, dimethyl methylphosphonate, dimethyl pentylphosphinate, diphenyl methylphosphonate, diphenyl methylphosphine, dibenzyl methylphosphine, dimethyl tolylphosphine, dimethyl phosphinate, diphenyl methylphosphine, diphenyl phosphinate, benzyl triphenylphosphine, benzyl phosphinate, benzyl triphenylphosphine and benzyl triphenylphosphine.

Reinforcing materials may also be used in the polyesteramide compositions of the invention. The reinforcing materials may include carbon filaments, silicates, mica, clay, talc, titanium dioxide, calcium carbonate, wollastonite, glass flakes, glass beads and fibers, and polymeric fibers and combinations thereof.

In another embodiment, the polyesteramide of the invention may be combined with other thermoplastic polymers to provide a blend to enhance or attenuate one particular performance characteristic or another. Thus, in another embodiment, the polyesteramide composition of the invention further comprises a polymer selected from the group consisting of:

(i) Polyester amides, which are different from those disclosed herein or have different diols, diamines and/or diacids, or

(ii) A polymer selected from one or more of the following: cellulose esters, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, poly (vinyl butyral), polyesters, polyamides, polystyrene copolymers, styrene acrylonitrile copolymers, acrylonitrile butadiene styrene copolymers, poly (methyl methacrylate), acrylic copolymers, poly (ether-imide)Polyphenylene oxide, polyphenylene sulfide, polysulfone ether, or poly (ether-ketone), ethylene vinyl acetate, thermoplastic polyurethane, polycarbonate, and ionomer polymers, such as those found in Surlyn ^TM Those sold under the product line (DuPont ).

In one embodiment, the polyester amide is present in about 1wt% to about 99wt% based on the total weight of the blend composition and the polymer (other than the polyester amide) is present in about 1wt% to about 99wt% based on the total weight of the blend composition. In one embodiment, the polyesteramide of the invention is present in an amount of about 5wt% to about 95wt% based on the total weight of the composition; the other polymers are present in an amount of about 5wt% to about 95wt% based on the total weight of the composition, although other amounts may be used depending on the desired characteristics.

In the following examples, viscosity was measured in tetrachloroethane/phenol (60/40, weight ratio) at 25 ℃ and calculated according to the following equation:

wherein eta _sp Is a specific viscosity and C is a concentration. The unit of inherent viscosity is deciliter per gram.

As mentioned above, the inherent viscosity of the polyesteramides of the invention is at least about 0.6dl/g. In certain embodiments, the inherent viscosity is at least about 0.8dl/g, in other embodiments at least about 1.0dl/g, in other embodiments at least about 1.2dl/g, and in other embodiments at least about 1.3dl/g. In other embodiments, the inherent viscosity is less than or equal to about 2.0dl/g. In addition, as noted above, inherent viscosities are described herein and are used as representative of the molecular weight of the polyesteramide. Such inherent viscosity parameters/molecular weight (Mn) are important for the desired end use characteristics and applications. Furthermore, in the polyester amide compositions and blend compositions, two additional important properties are impact properties and a relaxation modulus of 24 ℃ for one month, as further described below.

In a second aspect, the present invention provides a shaped or formed article comprising a polyesteramide composition as described herein. Such articles have a wide variety of potential end uses consistent with the end uses of currently existing thermoplastic resins having similar physical properties. Advantageously, the polyesteramides of the invention are capable of autoclaving. Accordingly, in another aspect, the present invention provides a shaped or formed article. Exemplary articles include films, sheets, containers, packaging materials, battery housings, medical device tubing, industrial articles, connectors, and the like.

In a third aspect, the present invention provides a layer, interlayer, sheet or film comprising the polyesteramide or polyesteramide composition disclosed herein. In certain embodiments, the polyesteramide may be amorphous, while in other embodiments, the polyesteramide may be semi-crystalline. Methods of forming layers, interlayers, sheets or films comprising the polyesteramide or composition described herein are well known in the art. Thus, these layers, interlayers, sheets, or films can be prepared from the polyesteramide or polyesteramide composition according to various embodiments of the invention using any suitable method including but not limited to extrusion, coextrusion, calendaring, compression molding, injection molding, and solution casting.

As used herein, the term "film" generally refers to a thin film. In some embodiments, such films can be rolled, while sheets refer to articles that are too thick to be rolled. In certain embodiments, the films of the present invention are about 20 microns to about 400 microns thick, or about 20 microns to about 80 microns thick, or about 40 microns to about 250 microns thick. In certain embodiments, the sheet of the present invention has a thickness of greater than about 400 microns, for example, about 1250 microns to about 0.75 inches.

As used herein, the term "interlayer" refers to a single or multi-layer polymeric sheet suitable for use in forming a multi-layer panel. The multi-layer panel is typically formed by: the sandwich is sandwiched between two substrates, which may be formed of a rigid material such as glass, and the assembly is laminated to form a multi-layer laminated panel. The multi-layer panel may be formed using a single layer or a multi-layer sandwich. As used herein, the terms "layer," "monolayer," and "monolithic" refer to interlayers formed from one single polymer layer, while the term "multilayer" refers to interlayers having two or more polymer layers adjacent to and contiguous with each other. As used herein, "layer" and "interlayer" are used interchangeably. Each polymer layer of the interlayer may comprise one or more polymer resins that have been formed into a sheet, optionally in combination with one or more plasticizers (depending on the type of polymer resin and the desired properties). The one or more polymer layers may also include additional additives, although these are not required. For multi-layer interlayers, particularly for multiple layers having different polymers or materials, the layers may be treated to improve interfacial adhesion, or additives such as silane-containing agents may be added to promote or improve adhesion between the layers. An adhesive layer or coating (e.g., tie layer) may also be used between the two polymer layers to improve adhesion between the layers, particularly between the different polymer layers.

Accordingly, in another aspect, the present invention provides a laminate structure comprising:

a. a top panel layer;

b. a polyesteramide composition comprising the following residues:

i. at least one diacid;

about 10mol% to about 90mol% of a glycol;

about 10 mole% to about 90 mole% of a diamine; and

a polyfunctional reactant having at least three functional groups selected from carboxylic acid, amine and hydroxyl groups; wherein the sum of diacid equivalents is about 100 mole percent and the sum of diol and diamine equivalents is about 100 mole percent; and

about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl groups, based on the total weight of the polyesteramide composition consisting of i.ii., iii.and optionally iv.wherein the polyesteramide exhibits an inherent viscosity of about 0.6dL/g to about 2.0 dL/g; and

c. a bottom panel layer.

The polymer composition used in the polymer interlayers as described herein may comprise one or more thermoplastic polymer resins, at least one of which is a polyesteramide composition of the invention. In some embodiments, the polyesteramide combination may be present in the polymeric layer in the following amounts based on the total weight of the polymeric interlayer: at least about 20wt%, at least about 25wt%, at least about 30wt%, at least about 35wt%, at least about 40wt%, at least about 45wt%, at least about 50wt%, at least about 55wt%, at least about 60wt%, at least about 65wt%, at least about 70wt%, at least about 75wt%, at least about 80wt%, at least about 85wt%, at least about 90wt%, at least about 95wt%, at least about 96wt%, at least about 97wt%, at least about 98wt%, or at least about 99wt% or more. When two or more resins are present, each resin may be present in the following amounts, based on the total weight of the polymer interlayer: at least about 0.5wt%, at least about 1wt%, at least about 2wt%, at least about 5wt%, at least about 10wt%, at least about 15wt%, at least about 20wt%, at least about 25wt%, at least about 30wt%, at least about 35wt%, at least about 40wt%, at least about 45wt%, or at least about 50wt%.

In certain embodiments, the glass transition temperature of the polyesteramide interlayer is about 0 ℃ to about 75 ℃. In certain embodiments, the glass transition temperature is about 67 ℃ to about 73 ℃, or 69 ℃ to 70 ℃, as measured by dynamic mechanical thermal analysis (dynamic mechanical thermal analysis, DMTA), as discussed further below.

The polyesteramides of the invention can be used as interlayers alone or in combination with layers comprising other thermoplastic polymers. Examples of suitable thermoplastic polymers may include, but are not limited to: polyvinyl acetal Polymers (PVA) (such as poly (vinyl butyral) (PVB) or isomers of poly (vinyl isobutyl) also known as PVB or PVisoB), aliphatic Polyurethanes (PU), poly (ethylene-co-vinyl acetate) (EVA), poly (vinyl chloride) (PVC), poly (vinyl chloride-co-methacrylate), polyesters, polyamides, polycarbonates, poly (methyl methacrylate) (PMMA), polyethylene, polyolefin, silicone elastomers, epoxy resins, ethylene-acrylate copolymers, poly (ethylene-co-butyl acrylate), and acid copolymers such as ethylene/carboxylic acid copolymers and ionomers thereof, derived from any of the foregoing possible thermoplastic resins, combinations of the foregoing, and the like.

The EVA polymer (or copolymer) may contain varying amounts of vinyl acetate groups. The desired vinyl acetate content is typically between about 10mol% and about 90 mol%. EVA with lower vinyl acetate content can be used for low-temperature sound insulation. Ethylene/carboxylic acid copolymers are typically poly (ethylene-co-methacrylic acid) and poly (ethylene-co-acrylic acid) having a carboxylic acid content of 1 to 25 mole%. Ionomers of ethylene/carboxylic acid copolymers can be obtained by partially or fully neutralizing the copolymer with bases such as hydroxides of strong alkali metals (e.g., sodium) and alkali metals (e.g., magnesium), hydroxides of ammonia or other transition metals (e.g., zinc). Examples of suitable ionomers includeIonomer resins (commercially available from DuPont (DuPont) of wilmington, tela). In some embodiments, the thermoplastic polymer may be selected from the group consisting of: poly (vinyl acetal) resins, poly (vinyl chloride), poly (ethylene-co-vinyl) acetates, and polyurethanes, while in other embodiments the polymer may comprise one or more poly (vinyl acetal) resins. When the interlayer comprises more than one polymer layer, each layer may comprise the same type of thermoplastic polymer resin, or one or more layers may comprise at least one different type of resin.

The layer or interlayer may also be used with other types of polymers or polymer layers such as cellulose esters, polyvinyl chloride, nylon, polyesters, polyamides, polystyrene, polycarbonate, polystyrene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, poly (methyl methacrylate), acrylic copolymers, poly (ether-imide), polyphenylene oxide, polyphenylene sulfide, polysulfone ether, polycarbonate, or poly (ether-ketone) of an aromatic dihydroxy compound.

Thermoplastic polymer resins for one or more layers (other than the polyesteramides of the invention) may be formed by any suitable method. In an embodiment, when the thermoplastic polymer resin comprises a poly (vinyl acetal) resin,such resins may be formed by acetalizing poly (vinyl alcohol) with one or more aldehydes in the presence of a catalyst according to known methods, such as, for example, U.S. Pat. nos. 2,282,057 and 2,282,026, and Wei De B (2016)High molecular science and technology encyclopedia"vinyl acetal Polymer", pages 1-22 (John Willi parent-child publishing company) (Wade, B. (2016), "Vinyl Acetal Polymers",Encyclopedia of Polymer Science and Technology,pp.1-22(John Wiley&sons, inc.) are incorporated herein by reference. The resulting poly (vinyl acetal) resin can include residues of at least one aldehyde in the following amounts, measured as percent acetalization of the resin according to ASTM 1396: at least about 50wt%, at least about 60wt%, at least about 70wt%, at least about 75wt%, at least about 80wt%, at least about 85wt%, or at least about 90wt%. The total amount of aldehyde residues in the poly (vinyl acetal) resin may be collectively referred to as the acetal content, with the remainder of the poly (vinyl acetal) resin being residual hydroxyl groups (e.g., vinyl hydroxyl groups) and residual ester groups (e.g., vinyl acetate groups), as will be discussed in further detail below.

Suitable poly (vinyl acetal) resins can include residues of any aldehyde, and in some embodiments, can include at least one C ₄ -C ₈ Residues of aldehydes. Suitable C ₄ -C ₈ The aldehyde may include: such as n-butyraldehyde, iso-butyraldehyde (also known as iso-butyraldehyde), 2-methylpentanal, n-hexanal, 2-ethylhexanal, n-octanal, and combinations thereof. The one or more poly (vinyl acetal) resins used in the layers and interlayers described herein can include at least about 20wt%, at least about 30wt%, at least about 40wt%, at least about 50wt%, at least about 60wt%, or at least about 70wt% of at least one C based on the total weight of aldehyde residues of the resin ₄ -C ₈ Residues of aldehydes. Alternatively or additionally, the poly (vinyl acetal) resin can include not greater than about 99wt%, not greater than about 95wt%, not greater than about 90wt%, not greater than about 85wt%, not greater than about 80wt%, not greater than about 75wt%, not greater than about 70wt%, or not greater than about 65wt% of at least one C ₄ -C ₈ Aldehydes. C (C) ₄ -C ₈ The aldehyde may be selected from the group listed above, or it may be selected from positiveButyraldehyde, isobutyraldehyde, 2-ethylhexanal, and combinations thereof.

In various embodiments, the poly (vinyl acetal) resin can be poly (vinyl butyral) (PVB) resin that is predominantly derived from n-butyraldehyde residues, and can include, for example, no greater than about 30 wt.%, no greater than about 20 wt.%, no greater than about 10 wt.%, no greater than about 5 wt.%, no greater than about 2 wt.%, or no greater than 1 wt.% aldehyde residues other than n-butyraldehyde. In general, aldehyde residues other than n-butyraldehyde present in the poly (vinyl butyral) resin can include: isobutyraldehyde, 2-ethylhexanal, and combinations thereof. When the poly (vinyl acetal) resin comprises a poly (vinyl butyral) resin, the weight average molecular weight of the resin can be: at least about 30,000, at least about 40,000, at least about 50,000, at least about 65,000, at least about 75,000, at least about 85,000, at least about 100,000, or at least about 125,000 daltons, and/or not greater than about 500,000, not greater than about 450,000, not greater than about 300,000, not greater than about 350,000, not greater than about 300,000, not greater than about 250,000, not greater than about 200,000, not greater than about 170,000, not greater than about 160,000, not greater than about 155,000, not greater than about 150,000, not greater than about 140,000, or not greater than about 135,000 daltons, as measured by size exclusion chromatography in tetrahydrofuran using Cotts and the Ouano low angle laser scattering (size exclusion chromatography using low angle laser light scattering, SEC/LALLS) method.

In general, the poly (vinyl acetal) resin can be prepared as follows: poly (vinyl alcohol) is formed by hydrolyzing poly (vinyl acetate) to poly (vinyl alcohol) and then acetalizing the poly (vinyl alcohol) with one or more of the above aldehydes. During hydrolysis of the poly (vinyl acetate), not all acetate groups are converted to hydroxyl groups and, therefore, residual acetate groups remain on the resin. Similarly, not all hydroxyl groups are converted to acetal groups during acetalization of poly (vinyl alcohol), which also leaves residual hydroxyl groups on the resin. Thus, most poly (vinyl acetal) resins include residual hydroxyl groups (e.g., vinyl hydroxyl groups) and residual acetate groups (e.g., vinyl acetate groups) as part of the polymer chain. As used herein, the terms "residual hydroxyl content" and "residual acetate content" refer to the amount of hydroxyl and acetate groups, respectively, that remain on the resin after processing is complete. The residual hydroxyl content and residual acetate content are both expressed in wt% based on the weight of the polymer resin and are measured according to ASTM D-1396.

The one or more polymer interlayers can further comprise at least one plasticizer. When present, the plasticizer content of one or more of the polymer layers may be: at least about 2, at least about 5, at least about 6, at least about 8, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, at least about 60, at least about 65, at least about 70, at least about 75, or at least about 80 parts per hundred resin (parts per hundred resin, phr), and/or no greater than about 120, no greater than about 110, no greater than about 105, no greater than about 100, no greater than about 95, no greater than about 90, no greater than about 85, no greater than about 75, no greater than about 70, no greater than about 65, no greater than about 60, no greater than about 55, no greater than about 50, no greater than about 45, no greater than about 40, or no greater than about 35phr. In some embodiments, the plasticizer content of one or more polymer layers may be: less than 35, no greater than about 32, no greater than about 30, no greater than about 27, no greater than about 26, no greater than about 25, no greater than about 24, no greater than about 23, no greater than about 22, no greater than about 21, no greater than about 20, no greater than about 19, no greater than about 18, no greater than about 17, no greater than about 16, no greater than about 15, no greater than about 14, no greater than about 13, no greater than about 12, no greater than about 11, or no greater than about 10phr.

Any suitable plasticizer may be used in the polymer layers described herein. The plasticizer may have a hydrocarbon segment of at least about 6 and/or not greater than about 30, not greater than about 25, not greater than about 20, not greater than about 15, not greater than about 12, or not greater than about 10 carbon atoms. Other examples of plasticizers may include phosphate esters, epoxidized oils, solid plasticizers, flame retardant plasticizers, and combinations thereof.

Any additional polymer interlayers can also include other types of additives that are capable of imparting specific characteristics or features to the polymer layer or interlayer. These additives may include, but are not limited to: adhesion control agent(adhesion control agent, "ACA"), dyes, pigments, stabilizers (e.g., UV stabilizers), antioxidants, antiblocking agents, flame retardants, IR absorbers or blockers, such as indium tin oxide, antimony tin oxide, lanthanum hexaboride (LaB) ₆ ) And cesium tungsten oxide, processing aids, flow enhancing additives, lubricants, impact modifiers, nucleating agents, heat stabilizers, UV absorbers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, enhancing additives, and fillers, as well as any of the foregoing additives. The specific type and amount of such additives may be selected based on the final characteristics or end use of the particular layer or interlayer.

Glass transition temperature (T) of polymeric material _g ) Is the temperature at which the material changes from a glassy state to a rubbery state. The glass transition temperature of the polymer layer can be determined by dynamic mechanical thermal analysis (dynamic mechanical thermal analysis, DMTA) according to the following procedure. The polymer sheet was molded into a sample disk of 8 millimeters (mm) diameter: the polymer sample disk was placed between two parallel plate test fixtures of Rheometrics dynamic spectrometer II (Rheometrics Dynamic Spectrometer II). The polymer sample trays were tested in shear mode at an oscillation frequency of 1 hz as the temperature of the sample was increased from 20 ℃ to 100 ℃ at a rate of 3 ℃/min. The position of the maximum value of tan delta (damping) plotted against temperature is used to determine the glass transition temperature. Experience has shown that this process is reproducible within +/-1 ℃. When the polymer layer or interlayer comprises two or more polymer layers, at least one of the layers may have a different glass transition temperature than one or more other polymer layers within the interlayer.

In some embodiments, interlayers described herein can include at least a first outer polymer layer and a second outer polymer layer. As used herein, the term "outer" refers to the outermost layer of the interlayer. Typically, the outer polymer layer is configured to be in contact with the substrate when the interlayer is laminated to the substrate, or with one of a pair of substrates when the interlayer is employed to form a multi-layer board. In some embodiments, each of the first and second outer polymer layers can include the respective first and second polyester amides disclosed herein (and optionally plasticizers or other additives). In some embodiments, each of the first and second outer polymer layers may include a poly (vinyl acetal) resin and optionally a plasticizer, and the resin may have a residual hydroxyl content and a residual acetate content within one or more of the ranges provided above. Similarly, each of the first and second polymer layers may include at least one plasticizer of the type and amount described above, such that the layer may also have a glass transition temperature as previously described. In other embodiments, the outer layer may also have an adhesive, coating or tie layer to facilitate bonding to a substrate (e.g., glass), depending on the polymer used in the layer.

According to some embodiments, the first outer polymer layer and the second outer polymer layer may be adjacent to and in contact with each other such that the first outer polymer layer and the second outer polymer layer are the only two layers of the interlayer. In other embodiments, at least 1, at least 2, at least 3, at least 4, or at least 5 or more polymer layers may be disposed between and in contact with at least one of the first and second outer polymer layers. When present, these additional layers may have similar or different compositions to each of the first and second polymer layers, and may include one or more of the polymers described above. In addition, as described above, the outer layer may also have an adhesive, coating, tie layer, or treatment to facilitate bonding to a rigid substrate (e.g., glass).

One or more of the layers may also be formed of other materials, such as a polymer film formed of polyethylene terephthalate (polyethylene terephthalate, PET), and the polymer film may include various metals, metal oxides, or other non-metallic materials or layers, and may be coated or otherwise surface treated. In some embodiments, one or more additional layers may include functional layers, including, for example, IR-reducing layers, holographic layers, photochromic layers, electrochromic layers, anti-friction layers (antilacerative layer), heating strips, antennas (antenna), solar radiation blocking layers, decorative layers, and the like.

In some embodiments, the interlayer may include at least a first polymer layer, a second polymer layer, and a third polymer layer, wherein the second polymer layer is disposed between and in contact with each of the first polymer layer and the third polymer layer. In certain embodiments, the first and third polymer layers can include at least one polyesteramide composition of the type and amount detailed previously, and the second (or intermediate) layer can include a different polyesteramide composition than previously. In certain embodiments, the first and third polymeric layers may comprise at least one polyesteramide composition of the type and amounts detailed previously, and the second (or intermediate) layer may comprise a different polymeric resin, such as polycarbonate. In other embodiments, the first and third polymer layers may comprise at least one poly (vinyl acetal) resin of the type and amounts detailed previously and optionally a plasticizer, and the second (or intermediate) layer may comprise a polyesteramide layer as previously described. In other embodiments, the first and third polymeric layers may comprise a polymeric resin (i.e., a non-polyester amide) that is at least different from the polyester amide disclosed herein, and the second (or intermediate) layer may comprise a polyester amide layer as previously described. Depending on the desired characteristics, the relatively "soft" (i.e., lower glass transition temperature) outer polymer layer may be sandwiched between "hard" (i.e., relatively higher glass transition temperature) inner layers, which may be advantageous for enhanced rigidity and impact resistance in a multi-layer panel formed from interlayers. Additional layers may also be included. Alternatively, an outer polymer layer that is relatively "hard" (i.e., higher glass transition temperature) may be sandwiched between inner layers that are "soft" (i.e., relatively lower glass transition temperature). Additional layers may also be included.

When three or more layers are employed in a multi-layer interlayer, some of the layers may be referred to as skin (or outer) layers and one or more of the layers may be referred to as core (or inner) layers. As used herein, "skin layer" generally refers to the outer layers of the interlayer and "core layer(s)" generally refers to the inner layer(s) disposed between the skin layers. At least one side of the core layer may be in direct contact with at least one side of the skin layer or may be in indirect contact with the skin layer through a tie layer, coating or adhesive.

Exemplary multi-layer interlayer embodiments include, but are not limited to: non-polyester amide// non-polyester amide; non-polyester amide// polyester amide; non-polyester amide// non-polyester amide; non-polyester amide// non-polyester amide; non-polyester amide//// polyester amide// non-polyester amide; polyester amide// non-polyester amide// polyester amide; polyester amide// non-polyester amide// polyester amide; polyester amide// non-polyester amide// polyester amide; or polyester amide// non-polyester amide// polyester amide.

In other embodiments, the multilayer structure may include 2 or more polyesteramide layers that are the same or different in composition, either by glass transition temperature, or both. For example, certain polyesteramide layers may have relatively low glass transition temperatures, while other layers may have relatively high glass transition temperatures. Exemplary multilayer structures may include, for example, polyesteramide T _g ¹ T of/(polyesteramide) _g ² T of/(polyesteramide) _g ³ Etc., wherein T is _g ¹ 、T _g ² 、T _g ³ … can each be independently selected from the group consisting of relatively low, relatively high and relatively intermediate T _g 。

In certain embodiments, -20 ℃ to-T _g ¹ 、T _g ² 、T _g ³ … is less than or equal to 200 ℃. Non-limiting examples include polyesteramides// high T _g Polyester amide// polyester amide; and polyesteramide// low T _g Polyester amide// polyester amide.

In each of these embodiments, the polyester amide layer may comprise a different polyester amide based on composition. Thus, any combination of the polyester amide layer with other polyester amide layers and/or non-polyester amide layers may be the same or different compositions. Other embodiments and permutations are possible as will be appreciated by those skilled in the art. The polyester and non-polyester amide layers may be any of the polymer layers described previously. Furthermore, additional coatings or layers, such as adhesives or tie layers, may be included in any embodiment, as desired.

In other embodiments, the layer or interlayer is a monolithic interlayer. In certain embodiments, the interlayer comprises at least two layers. In other embodiments, the interlayer comprises at least three layers, wherein at least one layer comprises a polyesteramide as described previously. In other embodiments, the interlayer comprises at least three layers, wherein at least two layers comprise a polyesteramide as described previously. In other embodiments, the interlayer comprises more than three layers, wherein at least one layer comprises a polyesteramide as described previously.

Layers and interlayers according to various embodiments of the present invention can exhibit enhanced properties as compared to conventional interlayers. For example, interlayers as described herein can exhibit high stiffness and good impact properties, while still maintaining suitable or even excellent optical properties, as compared to comparative interlayers used in construction applications. Thus, the interlayers described herein can be adapted for use in many structural and load-bearing applications, subject to various pressure, temperature changes, and impacts, while maintaining suitable performance and aesthetic values and characteristics.

Interlayers as described herein may exhibit enhanced rigidity. The stiffness of the polymer layer or interlayer can be characterized by its shear storage modulus (G') measured according to ASTM D4065-12 at 50 ℃ (and, in some cases, at other temperatures as described below). In some embodiments, a polymer layer or interlayer as described herein may have a shear storage modulus (G') at 50 ℃ of: at least about 4, at least about 5, at least about 10, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 70, at least about 80, at least about 90, at least about 100, at least about 110, at least about 120, at least about 130, at least about 140MPa, at least about 150MPa, at least about 160MPa, at least about 170MPa, at least about 180MPa, at least about 190MPa, at least about 200MPa, at least about 210MPa, or at least about 220MPa. There is no particular upper limit, although in practice, the layer or interlayer may exhibit a shear storage modulus of up to 250MPa or even up to 280MPa or more at 50 ℃.

In addition to enhanced rigidity, interlayers according to embodiments of the present invention can exhibit desirable impact resistance as characterized by the fracture height (or average fracture height) of the interlayer as measured by ANSI/SAE Z26.1-1996 when having a thickness of 30 mils and when laminated between two 3mm thick sheets of transparent glass at a temperature of about 70°f (about 21 ℃). In some embodiments, the fracture height of the interlayers described herein, measured as described above, is: at least about 12, at least about 12.5, at least about 13, at least about 13.5, at least about 14, at least about 14.5, at least about 15, at least about 15.5, at least about 16, at least about 16.5, at least about 17, at least about 17.5, at least about 18, at least about 18.5, at least about 19, at least about 19.5, at least about 20, at least about 20.5, at least about 21, at least about 21.5, at least about 22, at least about 22.5, at least about 23, at least about 23.5, at least about 24, at least about 24.5, or at least about 25 feet, at least about 25.5, at least about 26, at least about 26.5, at least about 27, at least about 27.5, at least about 28, or at least about 28.5 feet, or more. Fracture height may also be measured at other thicknesses. In the examples, the higher the fracture height, the better.

The values for the fracture height (or average fracture height) provided herein are obtained using an interlayer laminated between two 3mm thick glass sheets having a known thickness of 0.762mm (i.e., 30 mils or 30 gauge). The description of these parameter values is not intended to limit in any way the thickness of the interlayers described herein, or the construction of multiple layer panels according to embodiments of the present invention. Rather, the description of these parameter values is intended to provide an exact test for determining the impact resistance exhibited by the interlayer (measured as average fracture height), measured at a known thickness, and normalized to a constant thickness (e.g., 30 mils or 45 mils) if desired, so that different interlayers can be compared at the same interlayer thickness. In many examples herein, since only one interlayer was tested for material availability for a given composition, the data provided is only the fracture height and not the average fracture height.

Hammer adhesion (pummel adhesion) is another parameter that may be used to describe the interlayers disclosed herein. The hammer adhesion test measures the adhesion level of glass to interlayer in laminate structures. The adhesion of the interlayer to the glass has a great influence on the impact resistance and long-term stability of the glass-interlayer structure. In this test, the laminate was cooled to 0°f (-18 ℃) or conditioned to room temperature 70°f (21 ℃) and was manually hammered at 45 ° angles on steel plates with a 1 pound (0.45 kg) equivalent force hammer (i.e., with a hammer or with an automated instrument). The sample was then brought to room temperature and all broken glass not adhered to the interlayer was removed. The amount of glass left adhered to the interlayer was visually compared to a set of standards. The standards correspond to scales in which varying degrees of glass remain adhered to the interlayer. For example, substantially no glass adheres to the interlayer when the hammer criterion is zero. On the other hand, at a hammer blow standard of ten, substantially 100% of the glass remains adhered to the interlayer. Hammer values for similar samples were grouped and averaged. The recorded values illustrate the average hammering values for the group, as well as the maximum range of hammering adhesion ratings for each surface. The interlayers described herein can have a hammer adhesion rating of 2 or greater, or 9 or less, or from about 2 to about 9.

In addition to enhanced rigidity and impact properties, interlayers according to embodiments of the present invention also exhibit suitable optical properties, which can vary depending on the final end use. Transparency is a parameter used to describe the optical properties of the interlayers described herein and can be determined by measuring haze values or percentages. Haze values represent the quantification of light scattered by a sample as compared to the incident light. The polymer samples that had been laminated between two transparent glass sheets were tested for haze value using a haze meter, with each transparent glass sheet having a thickness of 3mm on a 30 gauge polymer sample (0.76 mm).

In certain embodiments, the percent (%) haze of a layer or interlayer is less than 5.0 (as measured on an interlayer having a thickness of 0.76 millimeters at an observation angle of 2 degrees, laminated with 3mm glass according to ASTM D1003-61 (re-approval 1977) -procedure B, using light source C. When the interlayer is used in a multi-layer panel that requires a high level of optical transparency, such as, for example, for a transparent window or windshield, the interlayer may be transparent or nearly transparent. In some embodiments, interlayers of the present invention can have a percent (%) haze value of less than about 5.0%, less than 4.5%, less than about 4.0%, less than 3.5%, less than 3.0%, less than 2.5%, less than 2.0%, or less than 1.5%, or less than 1.0%, or less than 0.5%, measured at a viewing angle of 2 degrees on an interlayer having a thickness of 0.76 millimeters and laminated with 3mm glass according to ASTM D1003-61 (re-approval 1977) -procedure B using light source C. In other embodiments, when haze is less important (or when a more opaque interlayer is desired), the interlayer may have a higher haze value, such as at least about 25%, at least about 30%, or at least about 40%.

Yellowness index ("YI") is another measure of optical quality for laminated structures. The yellowness index of a polymer sheet was measured as a function of spectrophotometric light transmittance in the visible spectrum by laminating (and autoclaving) a 30 gauge (30 mil or 0.76 mm) sheet sample between two sheets of 3mm clear glass using HunterLab UltraScan XE according to ASTM method E313 (formerly D-1925) (light source C, viewing angle 2 °). In certain embodiments, the layer or interlayer has an excellent color or yellowness index YI, measured according to ASTM method E313 (formerly D-1925) (illuminant C, viewing angle of 2). In various embodiments, the interlayer may exhibit a yellowness index of less than 2.5, less than 2.0, less than 1.5, less than 1.0, less than 0.75, less than 0.5, less than 0.4, or less than 0.3 according to ASTM E313.

Another parameter used to determine optical properties is the percent visible light transmittance (percent visual transmittance,%T _vis ) Which is measured on HunterLab UltraScan XE, hunterLab UltraScan XE is commercially available from Hunter Associates (raston, virginia). This value can be obtained by analyzing a 30 gauge polymer sample laminated between two sheets of transparent glass, each glass having a thickness of 3mm (available from pittsburgh glass, pa). In some embodiments, when a transparent multilayer panel is desired, the interlayers of the present invention can have the following percent visible light transmission: at least about 80%, at least about 81%, at least about 82%, at least about 83%, at least about 84%, at least about 85%, at least about 85.5%, at least about 86%, at least about 86.5%, at least about 87%, at least about 87.5%, or at least about 88%, at least about 88.5%, or more.

In certain embodiments, when the transparency and/or haze of the interlayer is not so important, the interlayer or a panel formed therefrom may be translucent, at least partially opaque, or completely opaque. Examples of applications for such panels include privacy glass or other similar end uses. According to some embodiments, such interlayers can have a haze value of, for example, greater than about 30%. Alternatively or additionally, the interlayer may have a visible light transmission of at least about 2%, at least about 5%, at least about 10%, and/or no greater than about 40%, no greater than about 35%, or no greater than about 30%. Additionally, in some embodiments, interlayers described herein can have the following reflectivity (%r) measured according to ASTM E-1164: greater than 5%, at least about 10%, or at least about 15%, and/or no greater than about 50%, no greater than about 45%, or no greater than about 40%. Other values of reflectivity, transmissivity, and haze are also possible depending on the particular end use. Further, the level of reflectivity, transmissivity, and haze may be controlled according to any suitable method, including, for example, inclusion of additives, colorants, dyes, and other similar components.

To determine the shear storage modulus (G') at 24℃for one month, a frequency sweep and a main curve (master cut) were constructed. Frequency scanning was performed on a Dynamic Mechanical Analysis (DMA) instrument according to the following procedure: the polymer sheet was molded into a sample pan with a diameter of 8 millimeters (mm). The polymer sample tray was placed between two parallel plate test fixtures of a Discovery HR-2 rheometer (TA Instrument). The polymer sample trays were tested in shear mode at a constant temperature over a frequency range of 0.01 to 100 hertz.

To construct the main curve to obtain the shear storage modulus (G') at 24 ℃ for one month data points, multiple frequency sweeps from 24 ℃ to 70 ℃ are required in 8 ℃ increments. After frequency scanning, the time-temperature superposition principle is applied using the Williams-Landel-Ferry (WLF equation) to determine the translation factor. At a given reference temperature (24 ℃ in this case), the main curve is generated and calculated by the TRIOS software provided by TA Instrument. Once the main curve at 24 ℃ is constructed, a shear storage modulus lasting 1 month can be obtained.

Shear relaxation modulus G (t): the principal curve of shear storage modulus can be converted to shear relaxation modulus using the approximation of the Ninomiya and Ferry equations:

G(t)＝G'(ω)-0.40*G”(0.40*ω)+0.014*G”(10ω)│ _ω＝1/t 。

Interlayers of the present invention can be formed according to any suitable method. Exemplary methods may include, but are not limited to, solution casting, compression molding, injection molding, melt extrusion, melt blowing, and combinations thereof. Multilayer interlayers comprising two or more polymer layers can also be prepared according to any suitable method, such as, for example, coextrusion, blown film, melt blowing, dip coating, solution coating, knife coating, paddle coating, air knife coating, print coating, powder coating, spray coating, lamination, and combinations thereof.

According to various embodiments of the invention, the layer or interlayer may be formed by extrusion or coextrusion. In the extrusion process, one or more thermoplastic resins, optionally plasticizers, and optionally one or more additives as previously described may be pre-mixed and fed into an extrusion device. The extrusion device is configured to impart a specific contoured shape to the thermoplastic composition so as to produce an extruded sheet. The extruded sheet, which is wholly at a high temperature and high viscosity, can then be cooled to form a polymer sheet. Once the sheet is cooled and solidified, it may be cut and rolled up for subsequent storage, transport and/or use as an interlayer.

Coextrusion is a process of simultaneously extruding multiple layers of polymeric material. Typically, this type of extrusion utilizes two or more extruders to melt different thermoplastic melts of different viscosities (or other characteristics) and deliver them through a coextrusion die at a stable volumetric throughput to the desired final form. In the coextrusion process, the thickness of the multiple polymer layers exiting the extrusion die can generally be controlled by adjusting the relative speed of the melt through the extrusion die, as well as by the size of the individual extruders processing each molten thermoplastic resin material.

The overall average thickness of the interlayer according to various embodiments of the invention may be: at least about 10, at least about 15 mils, at least about 20 mils, at least about 25 mils, at least about 30 mils, at least about 35 mils, at least about 40 mils, at least about 45 mils, at least about 50 mils, at least about 55 mils, at least about 60 mils, at least about 65 mils, at least about 70 mils, at least about 75 mils, at least about 80 mils, at least about 85 mils, at least about 90 mils, or greater, although other thicknesses are possible depending on the application and desired characteristics. In one embodiment, the overall average thickness of the interlayer will be from about 15 to about 90 gauge. If the interlayer is not laminated between two substrates, its average thickness may be determined by directly measuring the thickness of the interlayer using calipers (or other equivalent means). If the interlayer is laminated between two substrates, its thickness may be determined by subtracting the combined thickness of the substrates from the total thickness of the multi-layer panel. While the foregoing relates to the thickness of a single interlayer, it should be understood that two or more single interlayers may be stacked or otherwise assembled together to form a composite interlayer having a greater thickness, which may then be laminated between various types of substrates for certain end use applications.

In some embodiments, depending on the desired characteristics and end use, one or more of the polymer layers may have an average thickness as follows: at least about 1, at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30 mils, or more.

Interlayers according to various embodiments of the present invention can be used in multiple layer panels comprising a layer or interlayer and at least a substrate, with the interlayer laminated to the substrate. Any suitable substrate may be used, and in some embodiments, the substrate may be selected from the group consisting of: glass, polycarbonate, acrylic, and combinations thereof. Typically, the substrates in the multi-layer panels are formed of rigid and generally transparent materials, such as those listed above. However, in other embodiments, the multi-layer panel may include only one rigid substrate, an interlayer, and at least one polymer film disposed on the layers or interlayers, forming a multi-layer panel referred to as a "bilayer". In some embodiments, the interlayers for the bilayer may comprise a multi-layer interlayer, while in other embodiments, a monolithic interlayer may be used. In other embodiments, the polymer film may be included in a multi-layer panel having two rigid substrates, where the polymer film may be between two interlayers, such as being encapsulated between two layers of an interlayer. The use of polymeric films in a multi-layer panel as described herein can enhance the optical quality of the final panel while also providing other performance improvements, such as infrared absorption or reflection. Polymeric films differ from polymeric layers or interlayers in that the individual films do not provide the necessary puncture resistance and glass retention characteristics. The polymer film is typically thinner than the sheet and may typically have a thickness in the range of 0.001 to 0.25mm, although other thicknesses may be used. Poly (ethylene terephthalate) ("PET") is one example of a material used to form a polymer film. Examples of suitable bilayer constructs include: (glass)/(interlayer)/(film), and (glass)/(interlayer)/(coating film). Examples of other constructs that may employ a polymer membrane (but not a bilayer) include: (glass)/(interlayer)/(film)/(glass), and (glass)/(interlayer)/(film)/(multilayer interlayer)/(glass), wherein the polymer film may have a coating or any other functional layer, as described above.

In an embodiment, the layers and interlayers will be used in a multi-layer panel comprising two substrates, such as, for example, a pair of glass sheets, with the interlayer disposed between the two substrates. Any suitable type of glass may be used to form the rigid glass substrate, such as alumina-silicate glass, borosilicate glass, quartz or fused silica glass, low-iron glass, and soda lime glass. The glass substrate may be annealed, thermally strengthened or tempered, chemically tempered, etched, coated or strengthened by ion exchange, or it may have been subjected to one or more of these treatments. The glass itself may be a rolled glass, float glass or flat glass. The glass may have a coating such as a metal coating, an infrared reflective coating, etc., or it may simply be a tinted or dyed glass. Examples of such constructs are: (glass)/(interlayer)/(glass) or (glass)/(interlayer)/(glass), wherein the interlayer may comprise a monolithically layered interlayer or a multi-layered interlayer as described herein. As previously described, the construct may also include one or more polymeric films, if desired, and each interlayer may be a monolithic or multi-layered interlayer, if desired. The thickness of the substrate may be in the range of 0.1mm to 15mm or more, and each panel may have the same thickness, or the panels may have different thicknesses.

A typical glass lamination process comprises the steps of: (1) assembling two substrates and an interlayer; (2) Heating the assembly by IR radiation or convection means for a first short period of time; (3) Transferring the assembly into a pressure roll for a first degassing; (4) Heating the assembly for a short period of time (such as to about 60 ℃ to about 120 ℃) to provide the assembly with sufficient temporary adhesion to seal the edges of the interlayer; (5) Feeding the assembly into a second pressure roller to further seal the edges of the interlayer and allow further processing; and (6) autoclaving the assembly at an appropriate temperature (such as 135 ℃ to 150 ℃) and pressure (such as 150psig to 200 psig) for an appropriate time (such as about 3490 minutes), depending on the actual construct and materials used. Other methods of degassing a interlayer-glass interface according to one of the embodiments of steps (2) through (5) above include vacuum bagging and vacuum looping methods, and both may also be used to form the interlayers of the present invention described herein.

The panels may be used in a variety of end use applications including, for example, windshields and windows for automobiles, railways, boats, or aircraft, structural building panels in buildings or stadiums, decorative building panels, hurricane glass, bullet resistant glass, and other similar applications. Examples of suitable building applications for panels according to embodiments of the present invention may include, but are not limited to: indoor or outdoor stairways or landings, road or sidewalk skylights, balustrades, curtain walls, floors, balconies, unilateral balconies, canopies, support beams, glass wings (fin) (which may be decorative and/or support structures), support posts, windows, doors, skylights, privacy barriers, shower doors, windows for high-rise buildings and architectural entrances, windshields for transportation applications (e.g., automobiles, buses, jet engines, trains, armored vehicles), bullet-proof or bullet-proof glass, safety glass (e.g., for banks), hurricane or hurricane-proof glass, aircraft cabins, mirrors, solar panels, flat panel displays, and explosion-proof windows. The glass laminate may be visually transparent, translucent, frosted, etched, or patterned.

In one embodiment, the interlayer is a monolithic interlayer comprising a polyester amide layer comprising a polyester amide or polyester amide composition disclosed herein. In one embodiment, the interlayer is a multilayer interlayer comprising at least a polyester amide layer comprising a polyester amide or polyester amide composition disclosed herein. In one embodiment, the interlayer is a multilayer interlayer comprising more than one polyester amide layer comprising a polyester amide or polyester amide composition disclosed herein. As previously mentioned, other polymeric layers, adhesive layers, tie layers, coatings, and the like may be included in the interlayer.

In certain embodiments, the multilayer interlayer further comprises at least one non-polyester amide layer. In certain embodiments, an adhesive coating may be used, wherein the adhesive coating is at least partially interposed between the non-polyester amide layer and the polyester amide layer. In certain embodiments, an adhesive layer (such as EVA or TPU) may be used between the layers of the multi-layer interlayer, or partially disposed between the layers of the multi-layer interlayer. In certain embodiments, the multi-layer panel comprises a layer or interlayer, optionally with other layers or interlayers.

The present invention may be further illustrated by the following examples of preferred embodiments thereof, but it should be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless specifically indicated otherwise.

Examples

Abbreviations:

AD is adipic acid; AZ is azelaic acid; 1,4-BDO is 1, 4-butanediol; d (D)DA is 1, 12-dodecanedioic acid; 1,4-CHDA:1, 4-cyclohexanedicarboxylic acid; 1,3-CHDA:1, 3-cyclohexanedicarboxylic acid; ECTMS is trimethoxy [2- (7-oxabicyclo [4.1.0 ]]Hept-3-yl) ethyl]A silane; GPTMS is (3-glycidoxypropyl) trimethoxysilane; the H2-dimer is hydrogenated dimer acid (Pripol) ^TM 1009 A) is provided; MACM:4,4' -methylenebis (2-methylcyclohexylamine), a mixture of isomers; MDEA is N-methyldiethanolamine; ODA is 1, 18-octadecanoic acid; PACM:4,4' -methylenebis (cyclohexylamine), mixtures of isomers; PTMG is polytetrahydrofuran diol; SE is sebacic acid; t928 is Tinuvin ^TM 928 (2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1, 3-tetramethylbutyl) phenol and TCDA is 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2.6 ]Decane; TMCA: 5-amino-1, 3-trimethylcyclohexane methylamine; TMP is trimethylolpropane; CHDMA:1, 4-bis (aminomethyl) cyclohexane; 1,3-CHDMA is 1, 3-bis (aminomethyl) cyclohexane; TMCD:2, 4-tetramethyl-1, 3-cyclobutanediol; CHDM:1, 4-cyclohexanedimethanol, MPMD is 2-methylpentyldiethyl diamine, min: minutes; TMHD is a mixture of 2, 4-trimethylhexane diamine and 2, 4-trimethylhexane diamine.

Gel Permeation Chromatography (GPC)

GPC analysis was performed on an Agilent series 1100GPC/SEC analysis system with a UV-Vis detector and a refractive index detector. The column set used was a polymer laboratory (Polymer Laboratories) 5 μm HFIP gel column and a guard. The eluent consisted of hexafluoroisopropanol and 20mM tetraethylammonium nitrate. The test was performed at 35℃at a flow rate of 0.8 mL/min. The instrument was calibrated with monodisperse polymethyl methacrylate standards (MW: 580 to 3,000,000). Samples were prepared by dissolving 20mg of the sample in hexafluoroisopropanol (10 mL). 10. Mu.L of isopropanol was added as a flow marker. The injection volume was 10. Mu.L. The results are reported as polymethyl methacrylate equivalent molecular weights.

Example 1: synthesis of polyesteramide by adding CBC

A500 mL round bottom flask equipped with a stainless steel stirrer, a glass polymer head allowing nitrogen/vacuum inlet, a glass arm (side arm) allowing removal of volatile byproducts, and a receiving flask was charged with dodecanedioic acid (92.1 g,0.40 mol), MACM (45.8 g,0.19 mol), 1,4-CHDM (30.9 g,0.215 mol), and TMP (0.13 g,0.001 mol). Titanium tetraisopropoxide solution (0.014 g/ml in butanol, 1096 μl) was added to provide a catalytic level of 100ppm elemental titanium based on theoretical polymer yield. The flask was purged twice with nitrogen before immersing the flask in a metal bath preheated to 180 ℃. After the contents reached a certain temperature, the stirrer was started and maintained at 200rpm under a gentle nitrogen sweep. The esterification/amidation was allowed to proceed for 40 minutes of condensate collection at 210 ℃, 30 minutes of condensate collection at 250 ℃, 50 minutes of condensate collection at 275 ℃. At the end of the esterification, a transparent colourless melt is obtained. The temperature was maintained at 275 ℃, the nitrogen flow was terminated, and replaced with a vacuum, which gradually decreased to 2 torr over 5 minutes. After 170 minutes, a clear pale yellow high-viscosity melt was obtained, the vacuum was replaced with nitrogen, and then 2.71 g of 13.7wt% CBC in xylene or 0.38mol% CBC was added. A suitable amount of foaming was observed and resolved before the vacuum was again reduced to 2 torr and held for 30 minutes with stirring at 25 rpm. After cooling to room temperature, the polymer was analyzed to give IhV of 1.28dl/g and GPC of 3.4 polydispersity.

Example 2: (comparative) Synthesis of Polyesteramide without chain extender

Autoclave of 1 gallon was usedTo produce polyesteramides, equipped with a stainless steel double screw stirrer, an electric heating mantle, a nitrogen inlet (nitrogen flow can be controlled by a thermal mass flow meter), a vacuum line outlet to a cold trap, an outlet to a condenser and back pressure regulator, pressure measurements and temperature measurements. The reactor was charged with dodecanedioic acid (921.2 g,4.0 mol), MACM (457.75 g,1.92 mol), 1,4-CHDM (307.51 g;2.13 mol), TMP (0.67 g;0.005 mol) and a solution of titanium tetraisopropoxide (0.64 wt.% in isopropanol, 7.19 g). The reactor was purged 3 times with nitrogen to preserve the reaction by using nitrogen and a continuous nitrogen flow of 2nL/hThe pressure inside the reactor was set at 2atm (1520 torr) under an inert atmosphere. The reaction mixture was heated to 80℃at which point the stirrer was started and maintained at 150rpm. The esterification/amidation was allowed to proceed for 30 minutes of condensate collection at 210 ℃, 30 minutes of condensate collection at 250 ℃, 40 minutes of condensate collection at 275 ℃. The temperature was maintained at 275℃and an additional amount of titanium tetraisopropoxide solution (0.64 wt% in isopropanol, 7.19 g) was added. The nitrogen flow was terminated and replaced with a vacuum, which gradually decreased to 0.75 torr over 20 minutes. The viscosity rise is qualitatively measured by monitoring the current consumption and stirring speed of the stirrer motor. The stirring speed was gradually reduced during the experiment to keep the current draw at the maximum allowable level (2 amps). After 275 minutes no further viscosity increase was observed and the reaction was run for an additional 15 minutes. After this period of time 850g of polymeric material were withdrawn from the reactor via the bottom discharge and cooled in a water bath. Analysis of the polymer gave an average IhV of 1.28dl/g and a GPC polydispersity of 3.1. Figure 1 gives a qualitative measure of the current/RPM ratio during the vacuum phase, i.e. the polymer viscosity, as a function of time.

Example 3: synthesis of CBC-added polyesteramide

The same experimental setup, procedure and raw material amounts as described in example 2 were used for this experiment. After a vacuum phase of 180 minutes, the vacuum was replaced with nitrogen and a quantity of CBC (21 w% in THF, 4.9g solution, 0.19mol% based on the final polymer) was added, instead of letting the reaction proceed until no further viscosity increase was seen. Five (5) minutes after the addition, the vacuum was reduced to 0.75 torr over 10 minutes. Seventy (70) minutes after CBC addition and therefore no further viscosity increase was observed after 250 minutes of the vacuum stage. The reaction was carried out for a further 15 minutes after which 690g of polymeric material were withdrawn from the reactor via a bottom discharge and cooled in a water bath. Analysis of the polymer gave an average IhV of 1.31dl/g and GPC polydispersity of 3.7. The current/RPM ratio during the vacuum phase as a function of time is given in fig. 1.

Results and further examples

Additional examples (4-13) were prepared using the procedure outlined in example 2 (comparative) and example 3, without or with different chain extenders, to confirm that high IhV polymers can be prepared with the introduction of chain extenders. Table 1 shows that in practice a high IhV can be achieved by using Eponex ^TM Epoxy 1510 (Hexion) or CBC chain extender. In example 4, eponex was used ^TM 1510 gives an IhV of 1.325, and in example 5, the use of CBC gives an IhV of 1.463.

Table 1: effect of chain extender on IhV

It appears that the introduction of chain extenders has a surprising effect on the time required to advance the polycondensation reaction to high IhV. Table 2 shows that the chain extender accelerates the reaction and a high IhV is obtained in a significantly shorter time under vacuum. As shown in example 6 of table 2, ihV was reached under vacuum within 207 minutes, in contrast to 290 minutes required to reach substantially the same IhV without the chain extender. Example 2 required about 40% more time under vacuum to obtain the same IhV as example 6, indicating that if a chain extender was used, the reactor productivity could be significantly increased.

Table 2: effect of chain extender on reaction time

A key advantage of laminated glass is its resistance to penetration when impacted by an object or when a person is thrown (or dropped) in an accident. One method of measuring the penetration resistance of laminated glass is to drop a 5 pound steel ball from different heights and record whether the ball penetrated the laminated glass panel. A series of experiments were performed in which laminated glass panels of 12 "by 12" (30 cm by 30 cm) were made using 3mm thick glass and an interlayer of approximately 0.762mm thick (0.030 "). The interlayer was compression molded to the target thickness using hot pressing, followed by lamination using a vacuum bag deaeration process and an autoclave. The composition of the interlayers tested is set forth in table 3. Resins for all interlayers were prepared according to the methods described in examples 2 and 3. Impact testing was performed at room temperature. Table 3 shows that the average fracture height of the laminated panels with interlayers (examples 6-8) prepared by adding the chain extender is higher than the control interlayer (example 2) prepared without the chain extender. All interlayers in table 3 have the impact properties required for laminated glass, but the impact properties are higher for those interlayers with chain extenders.

Table 3: effect of chain extender on average fracture height of laminated glass

In laminated glass, the optical properties of the interlayers are extremely important as they affect the visual quality of the laminated glass. The key such property is haze, and very low haze is a desirable property for interlayers and laminated glass panels. Table 4 shows that the haze advantageously remains at a low level of less than 2% (or even about 1% or less) despite the presence of a chemical reaction between the matrix material and the chain extender. The very low haze of all the formulations shown in table 4 indicates that the polymer remained amorphous despite the chain extension reaction and the haze was similar to that of the polymer without the chain extender.

Table 4: effect of chain extender on haze of laminated glass made with PEA interlayers

The haze values listed in Table 4 were measured on laminated glass made with 3mm float glass and a interlayer of the composition listed in Table 4 of 0.76mm (0.030 inch), and it can be seen that low haze values can be obtained regardless of the type or level of chain extender.

Another important property of laminated glass is the adhesion of the interlayer to the glass. High adhesion is desirable so that if the glass breaks, glass fragments and pieces will continue to adhere to the interlayer and minimize glass fall-off, ensuring personal safety and minimizing property damage. Table 5 shows the adhesion properties of several PEA interlayers prepared according to examples 2 and 3 and laminated using 3mm glass.

Table 5: the effect of the chain extender on the adhesion of the PEA interlayer to the glass, including the PVB control

The adhesion of the interlayer was measured at room temperature using the compression shear adhesion method. Compression shear adhesion ("CSA") measurements help characterize the adhesion level between materials. CSA measurements were made with a Alpha Technologies T-20 tensiometer equipped with a special 45 ° compression shear sample holder or clamp. The laminate was drilled into at least five 1.25 inch diameter trays and held at room temperature for 24 hours prior to CSA testing. To measure CSA, the tray is placed on the lower half of the clamp and the other half of the clamp is placed on top of the tray. The crosshead was advanced down at 3.2 mm/min, resulting in one piece of the disc sliding relative to the other. The compressive shear strength of a disc is the maximum shear stress (measured in megapascals ("MPa)) required to cause adhesion failure.

It can be seen that the introduction of the chain extender does not adversely or negatively affect adhesion. In contrast, the addition of the chain extender may have increased adhesion to the glass as compared to the control case of example 2, and it is comparable to or better than the control case of example 11, which contains a lower level of amide. All polyester amide interlayers have a ratio to control PVB interlayers commercially available from ishiman chemical company (Eastman Chemical Company) Structural (DG 41), higher adhesion.

Another weight of the structural glassThe desired interlayer characteristic is the relaxation modulus of the interlayer at a given temperature and time combination. Table 6 shows the effect of changes in% MACM levels of the material on the relaxation modulus at 24 ℃/1 month (examples 2 and 11). As can be seen from Table 6, the variation of MACM was observed for a relaxation modulus of 24℃for 1 month and a glass transition temperature (T _g ) Has a significant impact. MACM levels in Table 6 have been measured using DMTA techniques, which will T _g Associated with a relaxation modulus of 24 ℃/1 month. To determine these values, T from samples of several known MACM levels was used _g Values are used to establish a calibration curve and then based on the measured T _g Values calculate MACM levels.

All shear mode characterization measurements were performed using a TA Discovery HR-2 mixed rheometer, and measurements were performed on single layer dried raw samples punched through an 8mm circular die using an 8mm plate/plate geometry. To ensure good bonding between the test sample and the metal plate, each test sample was loaded at 65 ℃ for each frequency sweep and first heated to 150 ℃ under programmed pressure and then cooled to the test temperature. The strain varied from 0.01% at 20 ℃ to 0.1% at 70 ℃ based on the stiffness of the material, which was positive for maintaining all measurements within the linear viscoelastic regime. Measurements were made at about 10 ℃ increments from 20 ℃ to 70 ℃ using a frequency range of 0.01Hz to 100Hz, every nineteen 8 data points (33 data points per scan per temperature). Applying the time-temperature superposition principle to determine the translation factor a using the Williams-Landel-Ferry (WLF equation) _T . The main curves and corresponding translation factors at the different reference temperatures were established and calculated by TRIOS software provided by TA Instrument.

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The effect of the chain extender is also shown in table 6. Examples 6 and 9 show that even small levels of chain extender have a surprisingly positive effect. The MACM of example 6 was 47.5%, and one would normally expect its 24 ℃/1 month relaxation modulus to be somewhere between 10MPa and 60MPa of example 11 and example 2, and possibly approaching an interpolated value of 37.8 MPa. Surprisingly, its 24 ℃/1 month relaxation was 86MPa, an increase of 127% over the expected value based on its% MACM level. Example 6 contains 0.19% CBC, it is evident that the CBC chain extender promotes an increase in the relaxation modulus of 24 ℃/1 month. In addition, example 6 actually had almost the same IhV level as comparative example 2 and comparative example 11.

Similar effects are evident in example 9, which contains 0.38% Eponex chain extender. Based on the 47.7% MACM level of example 9, an interpolated value for a relaxation modulus of approximately 48.9MPa at 24 ℃/1 month was expected. As can be seen from table 6, the relaxation modulus at 24 ℃/1 month of example 9 is 80MPa, which is 63.4% higher than expected. In addition, ihV of example 9 was actually lower than that of comparative example 2 and comparative example 11. Typically, ihV is related to MW, so example 9 is expected to relax faster due to lower IhV (and MW), but due to Eponex ^TM The epoxy 1510 (Hexion) chain extender acts, which in effect shows a slower relaxation.

Table 7 shows the effect of the concentration of CBC chain extender on the molecular weight of the resulting polymer. It can be seen that as the CBC concentration increases, the Mw and Mz also increase, and very high Mw and Mz can be achieved, as shown in example 5. It can also be noted that if the amount of chain extender is increased, the polydispersity of the final polyesteramide increases.

Table 8 shows Eponex ^TM 1510 effect of concentration of chain extender on molecular weight of the resulting polymer. It can be seen that very high Mw and Mz can be obtained as shown in example 4, compared to the control (example 13).

The invention has been described in detail with particular reference to certain embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. A polyesteramide composition comprising the following residues:

a. at least one diacid;

b. about 10mol% to about 90mol% glycol;

e. About 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl groups, based on the total weight of the polyesteramide consisting of a, b, c and optionally d,

and wherein the polyesteramide exhibits an inherent viscosity of about 0.6dL/g to about 2.0 dL/g.

2. The polyesteramide composition of claim 1 wherein the diacid is selected from aliphatic dicarboxylic acids having 3-36 carbon atoms, cycloaliphatic dicarboxylic acids having 8-14 carbon atoms, and aromatic dicarboxylic acids having 8-16 carbon atoms.

3. The polyester amide composition of claim 1 wherein the diacid is selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid, glycolic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, suberic acid, and 2, 6-naphthalenedicarboxylic acid.

4. The polyesteramide composition of claim 1 wherein the diacid is a dimer acid selected from 9- [ (Z) -non-3-alkenyl ] -10-octylnonadecanoic acid and 9-nonyl-10-octylnonadecanoic acid.

5. The polyester amide composition of claim 1 wherein the glycol is selected from the group consisting of aliphatic glycols, cycloaliphatic glycols, and aralkyl glycols.

6. The polyesteramide composition of claim 1 wherein the glycol is selected from ethylene glycol; 1, 2-propanediol; 1, 3-propanediol; 1, 4-butanediol; 1, 5-pentanediol; 1, 6-hexanediol; 2, 2-dimethyl-1, 3-propanediol; 1, 2-cyclohexanedimethanol; 1, 3-cyclohexanedimethanol; 1, 4-cyclohexanedimethanol; 2, 4-tetramethyl-1, 3-cyclobutanediol; isosorbide; p-dibenzyl alcohol; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycol; dipropylene glycol; a dibutylene glycol; polyalkylene ether glycols selected from polypropylene glycol and polytetramethylene glycol.

7. The polyester amide composition of claim 1 wherein the diamine is selected from the group consisting of alkylene diamines having 2 to 12 carbon atoms, cycloalkylene diamines having 6 to 17 carbon atoms, and aromatic diamines having 8 to 16 carbon atoms.

8. The polyesteramide composition of claim 1 wherein the diamine is selected from 1, 2-ethylenediamine; 1, 6-hexamethylenediamine; 1, 4-cyclohexanediamine and 1, 3-cyclohexanediamine; 1, 4-cyclohexanedimethylamine and 1, 3-cyclohexanedimethylamine; 4,4' -methylenebis (cyclohexylamine); 4,4' -methylenebis (2-methylcyclohexylamine); and 2, 4-tetramethyl-1, 3-cyclobutanediamine; 2, 4-trimethylhexamethylenediamine; 4-oxaheptane-1, 4-diamine; 4, 7-dioxadecane-1, 10-diamine; 1, 4-cyclohexane dimethylamine; 1, 3-cyclohexane dimethylamine; 1, 7-heptamethylenediamine; and 1, 12-dodecamethylenediamine.

9. The polyesteramide composition of claim 1, wherein the multifunctional reactant is selected from trimellitic acid, trimellitic anhydride, trimesic acid, pyromellitic dianhydride, pentaerythritol, glycerol, trimethylol propane, trimethylol ethane, erythritol, threitol, dipentaerythritol, sorbitol, and dimethylol propionic acid.

10. The polyester amide composition of claim 1 wherein the chain extender is selected from the group consisting of difunctional compounds selected from the group consisting of diepoxides, diisocyanates, biscaprolactam, bisoxazolines, carbodiimides, and dianhydrides.

11. The polyesteramide composition of claim 1 wherein the number average molecular weight (Mn) is greater than about 10,000 daltons.

12. The polyesteramide composition of claim 1 wherein the glass transition temperature (T _g ) From about 0 ℃ to about 200 ℃ as measured by dynamic mechanical thermal analysis.

13. A polyesteramide composition comprising the following residues:

a. a diacid selected from sebacic acid and dodecanedioic acid;

b. about 40mol% to about 60mol% 1, 4-cyclohexanedimethanol;

d. From about 0.1mol% to about 0.5mol% trimethylolpropane;

e. about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl, based on the total weight of the polyesteramide consisting of a, b, c and optionally d.

14. An interlayer comprising the polyesteramide composition of claim 1.

15. A multi-layer interlayer comprising:

a first layer comprising a polyesteramide composition comprising residues of:

a. at least one diacid;

b. about 10mol% to about 90mol% glycol;

e. about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino and hydroxyl groups, based on the total weight of the polyesteramide composition consisting of a, b, c and optionally d,

wherein the polyesteramide exhibits an inherent viscosity of about 0.6dL/g to about 2.0 dL/g; and

A second layer comprising a polymer composition different from the polyester amide composition of the first layer.

16. A laminate structure comprising:

a. a top panel layer;

b. a polyesteramide composition comprising the following residues:

i. at least one diacid;

about 10mol% to about 90mol% of a glycol;

about 10 mole% to about 90 mole% of a diamine; optionally, a third layer is formed on the substrate

A polyfunctional reactant having at least three functional groups selected from carboxylic acid, amine and hydroxyl groups;

from about 0.01wt% to about 10wt% of a chain extender reactive with a group selected from the group consisting of carboxyl, amino, and hydroxyl groups, based on the total weight of the polyesteramide composition consisting of i., ii., iii, and optionally iv, wherein the polyesteramide exhibits an inherent viscosity of from about 0.6dL/g to about 2.0 dL/g; optionally, a third layer is formed on the substrate

c. A bottom panel layer.

17. The laminate structure of claim 16 wherein the panel comprises glass.

18. A shaped or formed article comprising the polyesteramide of claim 1.

19. The article of claim 18, wherein the article is selected from the group consisting of a film, a sheet, a container, a packaging material, a battery housing, a medical device tubing, an industrial article, and a connector.